Preparation of silica-alumina,titania-alumina,and phosphorous oxide-alumina catalysts



United States Patent PREPARATION OF SILICA-ALUMINA, TITANIA- ALUMINA, AND PHOSPHOROUS OXIDE-ALU- MINA CATALYSTS Marvin F. L. Johnson, Homewood, Norman J. Williams, Park Forest, and Robert A. Sanford, Homewood, Ill., assignors to Sinclair Research, Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 28, 1965, Ser. No. 505,472

Int. Cl. B01j 11/40, 11/32; Cg 11/04 U.S. Cl. 252-437 11 Claims ABSTRACT OF THE DISCLOSURE A new process has been discovered for the preparation of highly acidic silica-alumina, titania-alumina and phosphorous oxide-alumina catalysts and supports. The process includes heating, preferably under reflux, and reaction in an inert organic solvent, of a solid, uncalcined, hydroxyl containing alumina having at least about 15 to 40 percent vaporizable material and having a surface area of at least about 300 mf /gm. with one or more of the following esters:

The present invention is directed to a method of preparing acidic catalysts and supports. More specifically, it is directed to-the preparation of catalysts comprised of alumina in chemical combination with oxides of silicon, boron, titanium or phosphorus.

Silica-alumina, boria-alumina, .titania-alumina and phosphorus oxide-alumina compositions can be used as hydrocarbon cracking catalysts or as catalyst supports, for example in hydrogenation, denitrogenation or hydrocrackingcatalysts containing metals such as a hydrogenation component or dual function metal catalyst components. A source of the activity in these catalysts is known to reside at least in part in their acidity; for example, when employing a silica-alumina support platinum catalyst is hydrocracking, olefins are considered to be produced at platinum sites, cracked at acidic sites, and the products hydrogenated at the platinum sites. An increase of. acidic sites on the catalyst surface, therefore, will yield' a corresponding increase in cracking activity.

conventionally, silica-alumina, titania-alumina, etc., are prepared by a coprecipitation-process or bythe addition of-alumina or an aluminum salt to a hydrogel of the other inorganic oxide, e.g., in the case of silica-alumina, a silica hydrogen, followed by washing and drying. Major 3,502,595 Patented Mar. 24, 1970 drawbacks in inorganic oxide-alumina composites prepared by these conventional processes are that they are limited insofar as the type of pore structure they are able to provide, in their ability to disperse promoters on the surfaces of the inorganic oxide-alumina support and in their ability to provide a high incidence of acidic sites.

A process has now been discovered which enables the preparation of highly acidic silica-alumina, boria-alumina, titania-alumina and phosphorus oxide-alumina compositions having a wider variety of pore structures than those from conventional preparations. Furthermore, the process of the invention offers the advantage of enabling greater dispersion of catalytic promoters when the inorganic oxide-alumina compositions are to be employed as catalyst supports.

In accordance with the present invention a solid hydroxyl-containing alumina is reacted with one or more of the following esters:

Ti(OR) The alumina with which the ester is reacted is a solid,

adsorptive, hydroxyl-containing alumina due to being. at least slightly in a state of hydration. The alumina can be, for instance, a hydrate alumina such as amorphous hydrous alumina, alumina monohydrate, alumina trihydrate or their mixture, or a calcined alumina such as an alumina of the gamma family. Often the calcined or activated aluminas will have a minimum loss on ignition of at least about 1 weight percent, i.e. the percent by weight of vaporizable material (percent V.M.) at 1000" C. The alumina is, however, preferably uncalcined and advantageously, in order to provide an optimum number of acidic sites, contains a high surface area such as a surface area of at least about m. /gm., preferably greater than about 300 m. /gm., as determined by the BET adsorption technique, and should have at least 5% loss on ignition;

preferably the percent V.M. will be from about 15 to v 40%. The alumina can also contain small amounts of other solid oxides such as magnesia, natural or activated in an inert organic solvent such as isooctane with the desired amount of ester and heating to reflux with stirring until the reaction is essentially complete. The amount of solvent employed provides fluidity to the reaction mixture. Similarly, the particular solvent used can vary widely providing it be essentially inert to the reactants employed. Snitable liquid solvents include hydrocarbons, oxygenated organic materials such as ethers, esters, ketones, e.g., methyl ethyl ketone, etc. The reaction is conveniently carried out at temperatures from about 25 to 270 C., preferably about 80 to 250 C. Pressures from about 1 atmosphere to 25 atmospheres or more may be employed. The reacted slurry can be heated to distill off most of the solvent, and distillation may be followed by cooling, solvent washing and drying. If a more active :atalytic base is desired the dried product can then be calcined under conventional calcination conditions, e.g., at temperatures of about 800 to 1300 F. or more, preferably about 900 to 1050" F. Calcination is effective to convert the ester-alumina reaction product to its more active, chemically-combined inorganic oxide-alumina form.

In order to maximize the reaction of the ester with the groups, the presence of free water in the reaction mixture is to be avoided. For instance, in the case of the silicates, the alkoxysilanes, for example, hydrolyze even in neutral solutions, although more slowly than in acidic or basic media, to produce the corresponding silanols. Except for :he monosilanols, these in turn may polymerize to siloxanes which, on calcination, convert to uncombined silicon dioxide.

The amount of ester employed in the reaction can vary depending upon the amount of inorganic oxide desired in the finished inorganic oxide-aiumina composition. In ;urn the amount of inorganic oxide desired in the final :atalyst may depend upon the particular modifying oxide and upon the particular use to which the catalyst is to be gut. These amounts are well described in the art and Jsually embrace a major proportion of alumina and a minor proportion of modifying oxide, or vice versa. Thus, for example, in petroleum cracking catalysts comprising SiO and alumina a presence of at least about 5 weight )ercent of SiO advantageously from about 15 to 35%, nay be desired. Conversely, in other catalysts the silica nay be the predominant component, with the alumina king, for instance, in the approximate 15 to 35% range. in any event the amount of each of the reactants is sulfizient to exert a significant catalytic effect the final Jroduct, and usually will be sufficient to provide a mininurn of about 1 wt. percent of each in the final product.

Generally, the extent of reaction of the ester with the groups of the alumina base varies directly with reaction emperature, reaction time and the percent of vaporizable material in the alumina base. Infra-red studies of the relClIlOIl products. also reveal that calcination thereof pro- 'ides additional bonding between the ester and the alunina, the increase in bonding being proportional to the everity of the calcination temperature. Thus, with ethyl lrthosilicate-alumina reaction products, for instance, the ndicative infra-red absorption band was shifted from 072 cm. for products calcined at 500 F. to 1030 cm. or those calcined at 1050" F. The extent to which the and decreases from 1100 cnif is an indication of the xtent of interreaction between silic acid esters and alumna.

As previously mentioned the process of the invention rovides advantage; in the dispersionpf catalytic promoters on the silica-alumina, boria-alumina, titania-alumina or phosphorus oxide-alumina support. For example, many" catalytic metal promoters such as platinum are more highly dispersed on alumina than on silica-alumina. Thus, in accordance with the present invention, advantage can be taken of aluminas greater dispersing ability by depositing the catalytic promoter on the alumina and then depositing the silica in accordance with the process of the present invention, i.e., reaction with the silicate, followed by calcining. When a catalytic promoter is provided in this manner it is preferred to calcine the composition prior to washing in order to avoid or reduce promoter loss via washing. Then after the silica, boria, titania or phosphorus oxide is chemically combined with the alumina the catalyst composition is again dried and calcined. Any of various promoters can be employed, such as, for insctance, the hydrogenation-denitrogenation catalytic metals of Groups IV, V, VI and VIIt of the Periodic Table such as chromium, tungsten, vanadium, iron, cobalt,

molybdenum, nickel, and the platinum series metals. The" promoting metals can be deposited on the substrate by various methods such as precipitation, coprecipitation, impregnation or mulling.

The following examples are included to further illustrate the present invention.

EXAMPLE I The alumina used as a starting material had a surface area of 446 m. /g. of A1 0 a 33.7% weight loss on ignition, i.e., weight percent of vaporizable material at 1000 C., and was identified by X-ray diffraction to consist of a mixture of amorphous hydrous alumina and" boehmite of 30 to 40A. crystallite size.

75 g. of this alumina and 300 ml. of isooctane were placed in a flask provided with a stirrer, reflux condenser and heating mantle. 51.6 ml. of ethyl orthosilicate were added to this mixture, an amount equivalent to 0.28 g. SiO per g. Al O The reaction mixture was refluxed with stirring for 3.75 hours. After cooling, the reflux condenser was replaced by an overhead condenser and 146.5 g. of distillate were collected; this distillate consisted of two phases, i.e., 22 g. of a dense phase and 119.5 g. of a lighter phase. 200 ml. of isooctane were added to the reaction slurry, which was allowed to stand overnight at room temperature before distilling another 81 g. of distillate which contained about 1 ml. of a dense phase. Each distillate was analyzed and found to.

contain ethanol, although much less in the second distillate; the total ethanol recovered in this way amountedv to 3.6 moles per mole of SiO deposited on the alumina. The silicated alumina was filtered, washed with 100 ml. of isooctane, dried in an oven at 110 C. and finally calcined for 3 hours at900" F. in a muflie furnace. 7

The product, designated 126, contained 17.6% SiO (ignited Weight basis) and had a surface area of 325 EXAMPLE II Al O After standing at room temperature for two days,

, 110.5 g. of a two-phase distillate was obtained, with a total ethanol content equivalent to 0.5 mole per mole of and had a surface area of 430 mF/g.

EXAMPLE III A silicated alumina was prepared essentially as de-' scribed in Example II, but with an equivalent quantity .of dimethyldiethorg silane; The product, designated1 14, I

agralyzed 77% SiO The infrared spectrgms of the calcined products of each of the foregoing examples showed a band in the 1200-1050 cm. region which can be distinguished from the 1100 cm.- band characteristic of pure silica or of conventional silica-alumina.

Among the alkoxysilanes, the reaction with hydroxylcontaining alumina occurs more readily as the number of alkoxy groups increases. For example, it is clear from Examples I-III that tetraethoxysilane (ethyl orthosilicate) is more reactive than the triethoxy compound, which, in turn, is more reactive than the diethoxy compound. For this reason, and because of its lower cost, ethyl orthosilicate is the preferred ester for preparing silicated alumina by the method of the present invention.

EXAMPLE IV 75 grams of the alumina of Example I, suspended in isooctane, in a'reaction flask equipped with reflux condenser and Stark tube, where heated under reflux until water ceased to collect in the Stark tube, thereby reducing the loss on ignition of the alumina to 22%, as calculated from the 11.5 ml. of water so collected. After this dehydration step, 51.6 ml. of ethyl orthosilicate were added, equivalent to 0.28 g. SiO per g. A1 and the mixture refluxed for 21 hours. After cooling to room temperature, the mixture was partially distilled to collect 61.3 g. of distillate, containing, ethanol equivalent to 1.7 moles per mole of-Si0 reacted. The solids were filtered, washed with 100 ml. of isooctane, dried at 110 C. and calcined for 6 hours at 900 F. The product, designated 57, analyzed 11.6% SiO and had a surface area of 362 mF/g.

' EXAMPLE V The alumina of Example I was calcined in a mufiie furnace at 900 F. to reduce its loss on ignition to. 1.9%. This was allowed to react with ethyl orthosilicate as in Example IV, without the dehydration step. The product, designated 184, analyzed 4.0% Si O It is clear from Examples I, IV and V that a reduction in the loss on ignition of alumina results in a lower reactivity thereof with ethyl orthosilicate.

EXAMPLE -VI v 25 grams of the alumina of 'Example'l," 24.6 ml. of ethyl orthosilicate, and ml. of isooctane were charged to a stirred autoclave. Air was removed by purging with nitrogen. The autoclave was heated 'to'212" C., and

maintained at this temperature for 15.5 hours. After EXAMPLE VII 25 grams of the alumina of Example I, calcined for 3 hours at 900 F. in a mufile furnace, 150 m1. of isopropanol, and 3.32 ml. of trimethylborate were placed in a flask provided with a stirrer, reflux condenser with drying tube and a heating mantle. The mixture was refluxed for approximately 8 hours and allowed to'stand about 8 hours at room temperature. The treated alumina was washed with isopropanol, oven dried at C., and calcined 3 hours at 900 E, in a muflle furnace. The product, designated 306, contained 2.8% B 0 75 grams of the alumina of Example I were suspended in isooctane and dehydrated to 22.1% V.M. by the technique described in Example IV. To the stirred mixture was added 72.9 g. of triethylphosphate. The reaction mixture was stirred at room temperature for 3 hours and then was heated to reflux temperature and refluxed 17 hours. The mixture was allowed to stand at room temperature for 3 days before the liquid was distilled oif. The treated alumina was solvent washed, oven dried, and calcined 3 hours in a muflle furnace. The calcined product, designated 75, analyzed 6.4% P0 'Table I summarizes the results of varying the tants and reaction conditions. The products of Examples IVIII, as Well as those of similar reactions, are described TABLE I Alumina Base Conditions Reaetant Vaporizable Alcohol Product material Gms. oxide recovered 3 after pre- (equivalent) Reaction (mols/mol Oxide Sample. Area, treatment, per gr'n. Temper-a reacted of content, Area, Example No m.2/g. Pretreatment wt.p ereent Ester alumina turez dioxide) wt.percent mJ/g. No.

None 33.7 (EtO)4Si 0.28(Si0) Reflux 3.6 17.6 (SiOz) .do 33.7 EtSi(0Et)a d 0.5 12.0 (310;) .do 33.7 MeiSi(OEt)z 7.7 (S192) Dehydration 22.0 (EtOhSi. 7 11.6 ($10,) Calcination,900F 1.9 (EtO)4 Si None 33.7 (EtO)4Si Calcination, 900 F. (MeO)|B Dehydration 22.1 (EtO)3PO do 22.0 (i-PrOh'li 33.7 (i-PrOhTi Water added 49.4 (1-PrO) T1 None 33.7 (Et0)4S1 .12 do- 33.7 (EtOhSr 0.28 do 7 83.7 (EtO)4Sl 0.39 Water added 48.6 (EtOh Si 0.39 None 33.7 (EtO)4S1 1.00 46 Calcination, 500 F 14.0 (EtO)4S1 0.28 Dehydration 23.0 (EtOhSi 0.28 do (EtO)4S1 0.28 do 22.4 (EtO)4Sl 0.28

None..." 33.7 (EtO)4Si 0.40

1 Before pretreatment.

2 With overnightstirring in isooctane solvent, followed by distillation of most of solvent and alcohol product.

3 Alcohol recovered in the distillat 4 Ignited weight basis.

5 After distillation of solvent, more solvent added for a second distillation.

Reacted 15.5 hours in stirred autoclave.

7 Isopropanol solvent.

B Methyl ethyl ketone solvent.

9 Dehydrated in methanol, reacted in isooctane. Reaeted 2 hours in stirred autoclave.

reac- The products of Examples I and II, and of other silicaaluminas prepared by the method of this invention were used as catalysts to test-crack a petroleum hydrocarbon East Texas gas oil fraction having the following approximate characteristics:

Aniline point, F 170 175 Pour point, F 35-40 Sulfur, percent 0.3

The results of the test cracking are given in Table II, wherein RA stands for relative activity, GP for gas factor, CF for coke factor and GG for gas gravity.

TABLE II.GAS-OIL CRACKING TEST DATASILICATED ALUMINA l Sample No 9054 9056 31 151 126 9059 9070 9071 Percent S102 10. 5 11. 7 12. 14.8 17.6 18.2 18. 7 21. 0 Virgin:

R.A 52. 85. 5 90.0 113.0 121.0 97. 5 83.0 96. 6 G.F 1. 05 1. 03 1.00 0.98 1.05 0. 95 0. 86 C.F 0. 91 1. 06 0. 92 1. 17 1. 06 0. 92 1. 02 G.G 1.06 1.16 1 17 1.23 1.22 1.18 1.31 1.41 Steamed (hrs 1 150 F 24 6 6 6 24 24 24 R .A. 75. 7 70. 5 77. 5 76. 3 73. 3 78.0 75. 5 G.F 0.93 1. 00 0. 93 0. 99 0. 95 0.90 0. 85 0.1. 0. 95 0. 94 0. 84 0.97 0. 79 0.96 l. 05 G.E 1.11 1.23 1.12 1.30 1 22 1.26 1.29 1.31 Surface Areas (m. /g.):

Virgin 340 360 430 325 319 298 306 Steamed 256 260 310 248 238 232 1 For details of preparation see Table 1. Prepared by impregnation with pure EtSi (OEt)3, drying, and calcining. 3.,

As illustrated in the foregoing Table II, the silicated aiuminas of the present invention are good cracking catalysts and provide moderately good product distributions. Although efiective as cracking catalysts at SiO concentrations as low as 5%, it is apparent that higher activities are obtained with SiO levels of about or more.

The steam treatment of the catalysts at 1150 F. was conducted for about 6 hours. Even after this degradative treatment most of the samples had a relative activity of 75 or better, indicating good stability thereof. It is noted ;hat the highest activity was obtained with Sample No. 126, which received the extra distillation during pregaration.

A micro-reactor technique was used for comparing :atalysts on the basis of their ability to crack heptene-2. [n this technique slugs of vaporized heptene-2 were inected into a helium carrier gas stream, over the catalyst, and into a gas chromatograph for analysis. This reaction was chosen as being representative of the cracking reictions occuring in hydrocracking, and heptene cracking :onversions are found to correlate with hydrocracking activities of the same supports promoted with platinum. Fhus, heptene-2 cracking can serve as a screening test "or hydrocracking supports. Table III shows results obained at 400 C. using 300 mg. of catalyst and He :arrier gas at a flow rate of 167 rnL/min. Isomerization o branched C olefins is ignored in calculating converion, and the weight percentage of the heptene-2 converted 0 C and C hydrocarbons was taken as cracking con- 'ersion.

TABLE III.CRACKING OF HEP- TENE-2 IN A PULSE INJECTION TYPE MICRO REACTOR Cracking Sample No. Percent S102 Conversion Control 0 381 5. 1 0. 393 8. 8 3. 4 9054 10. 5 6. 8 382 11. 0 12. 9 349 14. 2 26. 1 368 18. 2 37. 6 9070 18. 44. 5

The unmodified alumina base of the examples.

We claim:

1. A process for the production of an acidic, inorganic oxide-alumina composition which consists essentially of heating and reacting in an inert liquid organic solvent at a temperature of about to 250 C., an uncalcined hydroxyl-containing alumina having about 15 to 40 percent vaporizable material, and having a surface area of at least about 300 m. gm. with an ester selected from the group consisting of:

Ti(OR) and (RO) PO wherein R and R are hydrocarbon groups of up to 18 carbon atoms and x is an integer from 1 to 4, and separating resulting inorganic oxide-alumina composition from the solvent and alcohol produced by said reaction.

2. The process of claim 1 wherein the resulting inorganic oxide-alumina composition is calcined to an active catalytic state.

3. The process of claim 1 wherein R and R are alkyl groups of 1-8 carbon atoms.

4. The process of claim 1 wherein the ester is ethyl orthosilicate.

5. The process of claim 1 wherein the. ester is tetraisopropyl titanate.

6. The process of claim 1 wherein the ester is triethyl phosphate.

7. The process of claim 1 wherein the inert organic solvent is hydrocarbon.

8. The process of claim 7 wherein the separated inorganic oxide-alumina composition is calcined'to a more catalytically-active state. 7

9. The process of claim 7 wherein the reaction is conducted under reflux.

10. The process of claim 9 wherein the separated inorganic oxide-alumina composition is calcined to a more.

catalytically-active state.

11. The process of claim 10 wherein the solvent is isooctane.

References Cited UNITED STATES PATENTS 2,154,079 4/1939 Weiss 252-455 2,243,404 5/1941 Voorhies 252-455 2,394,796 2/ 1946 Marisic 252-455 2,422,884 6/ 1947 Burgin 252-432 2,428,741 10/1947 Plank 252-455 2,493,896 1/1950 Pardee et a1. 252-455 2,912,421 11/1959 Juveland et a1. 252-430 2,943,066 6/1960 Arnold et a]. 252-463 3,014,020 12/1961 Balthis 252-463 PATRICK P. GARVIN, Primary Examiner US. Cl. X.R. 

